Thermistors



March 21, 1961 Yogi-"O {CHIKAWA 2,976,505

THERMISTORS Filed Feb. 24, 1958 2 Sheets-Sheet 2 Aged uf I260C in Air Sinfered and Cooled n Neutral Gos Atmosphere B Fg.3. A

|03 E .C o E 2 g lo (D 03,0037 80.852 S'MT T'Os IO I l l l 50 IOO |50 200 250 300 Temperature "C Aged of |260C in Air |06- Y B0 TiO E .ol .99 3 F lg. 4. f ,O5

E .C o E |04- D No Aging l l l I 50 IOO |50 ZOO 250 300 Temperature C WITNESSESZ YINVENTOR MQ A065 Yoshlo Ichlkowo United States Patent() 2,976,505 vTHERMISlORS Yoshio Ichikawa, Swissvale, Pa., assignor to Westing- .house Electric Corporation, Eastk Pittsburgh, Pa., a

corporation of Pennsylvania i e Filed Feb. 24, 195s, ser. Nb.`1\17,191 8Claims. (Cl. 3378-22) invention relates to thermisto-rs comprising ceramic ,bodies `having 'a 'high' positive temperature coeficient of electrical resistance and processes for preparingV them:

rCeramic semiconductor materials are generally known,

- 'ance' occurs. f

'- Furthermore, theknown materials are characterized by In variabilityof Vresistivity at any temperature level. employing such semiconductor materials for temperature control purposes, the variability is so great that individual corrections must be applied to the material in each' device employing them.

` It Wouldl be desirable to have available a material that has a relatively constant predetermined resistivity over a range'of temperatures, for example, at room `temperature, and then a sudden increase in resistance within a selected range of temperatures `and almost abruptly reaches la resistance from l to 100 times greater in a matter of a few degrees. The room temperature resistivity should be controllable within rather close limits 4and the temperature at which Vthe resistance begins to rise abruptly likewise should be readily preselected and controllable with considerable accuracy so that individual calibrations and adjustments are device employing them.

Thermally sensitive ceramic bodies having a negative coeicient temperature of resistance lare commonly called thermistors Such thermistors are Widely employed in electrical and'electronic equipment for measuring temperatures, controlling temperatures, controlling a voltage for stabilizationof electrical current, for making thermal conductivity measurements and in numerous other applications. A thermistor material with a marked positive temperature coeicient of 'electrical resistance would be highly desirable for use in electronics and electrical equipment, since it would in many cases increase the accuracy of the devices andy vsimplify their construction. It is particularly desirable thatl these positive temperature coefficient thermistor materials be characterized by a veryabrupt rise in resistance in a range of a few degrees 4 of temperature'from a relatively constantlow-resistance to ,anextremelyhigh resistance. With such thermistor not required for each t Patented Mar. 2l, 1961;

materials, marked improvement in the electric devices could be made with considerable increase in sensitivity of the devices. Furthermore, much more precise and accurate control could be effected by use of such improved materials.'

The object of the present invention is to provide new thermistor materials having characteristics such that at low temperatures the electrical resistivity is substantially constant and upon reaching a lpredetermined temperature,

the electrical resistance increases abruptly so that in arange of a few degrees the electrical resistance will increase many times to a high value.

Another object of the invention is to prepare ceramic bodies having a marked positive temperature coeicient of electrical resistivity over a selected narrow range of temperatures, the body comprising a stoichiometric combinat-ion of titanium dioxide, and one of the group consisting of bariuml oxide, barium strontium oxide and barium lead oxides with controlled small amounts of trivalent rare earth metal oxides i'n order to produceA a` predetermined low temperature'resistivity.

. A still further object of the invention is to provide a process for preparing certain titanate ceramic bodies so` that the member will exhibit amarked positive temperature coefcient of resistivity within arel-ativelynarrow range of temperatures.

g Other` objects of the invention will in part be obvious and in part appear hereinafter.

For a better understanding of the nature and scope of` the invention, reference should be had to the following; in which:

Figure 1 is a view in elevation of a resistance member in accordance with the invention;

Fig. 2 is a graph plotting resistivity of a number of materials against temperature;

Fig. 3 is -a graph plotting resistivity against temperature for a material processed in several different and Fig. 4 is a graph plotting resistivity against temperature geneously combined and tired to form a ceramic body exhibiting a predetermined electrical resistance over a low range of temperatures and when heated to a selected temperature will exhibit an extremely high positive temperature coefficient of electrical resistance wherebythe resistance will increase, usually in a few times to a high upper resistance value.

In particular, the composition maybe varied and readily controlled so that the range of temperatures within which the `resistancebegins 'to rise may be 'selected rather closely and further the low temperature resistivity may be selected as desired. Thus, the` low temperature resistivity may be readily selected so that the resistance f in ohm-centimeters may be from a value as low as l0.A

ohm-centimeters to aboutl0,000 ohmcentimeters, 'the higher resistance' attained on heating to a selected i ways,

degrees, many 1 tium. oxide and leady oxide and (b) a small but critical proportion of cerium oxide and yttrium oxide. In preparing the'. compositions titanium dioxide, preferably anatase, is combined with barium oxide or a compound which willl engender barium oxide during tiring, for example, barium carbonate. The lead oxide and strontium oxide components may be added as such or the carbonate. The yttrium or cerium oxides may be added as the oxides or preferably the nitrates or oxalates thereof. The compounds are preferably of a high purity.

The correct proportions of the titanium dioxide, barium oxide or barium carbonate, and the yttrium or cerium containing materials, with or without the lead and strontium compounds are wet mixed, using water, in a porcelain ball mill in order to produce a homogeneous mixture. The resultant Kintimate admixture is dried as, for example, at 80 C. and then calcined while exposed to air in a refractory crucible, at a temperature of, for example, 1000 C. for ea period of hours. The calcined product comprises an intimate mixture of oxides of titanium, barium, yttrium or cerium, as Wellas lead oxide or strontium oxide if the latter is present. In order to assure the best results the calcined mixture of oxides is wet milled in a porcelain ball mill to an extremely ne slurry. Ball milling with ilint pebbles for a period of up to 16 hours has given good results. The slurry is dried and pulverized, if necessary, to pass through a 200 mesh sieve. In preparing ceramic bodies the resultantv tine powder may be admixed with a volatile organic binder, and the mixture with the binder is then pressed at a high pressure in a suitable die. Good results have been obtained when pressures of 5,000 to 50,000 lbs. per square inch were applied to the oxide powders. The pressed bodies are sintered in an inert atmosphere, preferably argon, at a' temperature to density the body or pellets. For barium titanate bodies, sintering temperatures of about 1470 C. to 1400 C. are suflicient. For barium lead titanates, the sintering temperatures may be some-v what lower, for example, 1120 C. to 1200 C.l It will be understood that at the lower temperatures longer times will be required; usually sintering for an hour or two is adequate. After sintering in the protective atmosphere the vitriied ceramic bodies are aged in air at a temperature of at least l000 C. to as high as 1350 C. for sev eral hours. This aging in air has been found to be critical in producing satisfactory thermistor devices.

More speciiically, it has been discovered that by adding strontium oxides to replace up to 30 mol percent of the barium oxides, the temperature at which the ceramic bodies will begin to abruptly increase in electrical resistance will beY progressively lowered. On the other hand, when lead oxide replaces a part or all of the barium oxidethe temperature at which the resistance of them both begins to increase abruptly is proportionally increased. The addition of the yttrium and cerium oxides to the composition causes the members tohave lower resistivity at, for example, room temperature, as the quantity thereof increases.

Particularly good results have been obtained with thev following compositions:

egresosY Y Particular attention is directed to the fact that in no case is there any molar excess of titanium dioxide over the combined total mols of barium oxide, barium stron-f tium oxide, or barium lead oxide and the cerium or yttrium oxides. The compositions are maintained with a close stoichiometric balance. The addition of silicon oxides and iron oxide has been found to be detrimental in amounts as low as 0.001 mol.

The following examples illustrate the practice of the invention.

p EXAMPLE I One mol of titanium dioxide, anatase, is-admixed with .94 mol of barium carbonate, 0.05 mol of lead carbonate and 0.01 mol of yttrium carbonate. The ingredients are wet mixed in water in a porcelain ball mill using flint pebbles for 2 to 4 hours. The slurry was dewatered andl then dried at C. in air. The dry powder was placed in a zirconia crucible and then heated in a furnace for 2 hours at a temperature of 1000 C. 'Ihe calcined proddisposed on a zirconia plate for 2 hours. Thereafter, thev vitriiied pellet was Withdrawn and then was placed within a circulating air furnace and aged at 1250 C. for 2 hours.

'Ille resistivity of the resulting pellet was determined by placing electrodes comprising an alloy of indium, lead, and silver, for example, 10% indium, 80% lead, and 10% silver, on both faces and ultrasonically soldering the alloy thereto. The room temperature resistivity up to approximately C. was 200 ohm centimeters. At approximately C. the resistivity began to rise rapidly so that at C. the resistivity was approximately 7000 ohm centimeters. Thereafter the resistivity rose more reaching a maximum of approximately 30,000 ohm centimeters at about C. where the resistivity leveled o", and at higher temperatures it began to drop.

By modifying the proportion of the composition of Example I to increase the lead to 0.1 mol while the barium comprised .89 mol, the yttrium remaining at .01 mol, there resulted a composition which has a relatively uniyforrn resistivity of approximately 75 ohm centimeters at room temperature and up to temperatures of about 12,09 C. At 125 C. the resistivity increases'rapidly With temperature rising as rapidly as the composition ofExample oo. a total of resistivity of 3000 ohm centimetersv at Example Il A composition was prepared from 1 mol of titanium dioxide (anatase), 0.74 mol barium oxide, 0.25 strontium oxide, and .01 yttrium oxide and vitried and air aged pellets were prepared following the procedure of Example I. Up to a temperature of approximately 25 C. the

The resultingv resistivity ofthe compositionwas approximately 4800 ohm centimeters. At a temperature of 30 C. the resistivity began to increase rapidly so that at a temperature of 70 C. the resistivity was 10,000 ohm centimeters. At approximately 175 C. the resistivity had `leveled off at a value of approximately 90,000 ohm centimeters and thereafter dropped slightly.

Referring to Fig. l of the drawing; there is illustrated a thermistor device which' comprises a ceramic body 12 prepared as disclosed herein, of the vitriiied and aged ceramic composition of thisinvention. To the upper face of the body 12 is aixed a contact layer 14 composed of a suitable metal or alloy or other good electrical conducting material into ohmic contact with the body 1.2. It will be understood that the layer 12 may be applied by soldering, brazing or other suitable techniques providing, however, that there be a very low resistance between the surfaces of the body 12 and the layer 14. A suitable electrical lead 16 is aiixed to the layer 14. Similarly, a counterelectrode 18 is affixed to the lower surface of the body 12 and carries an electrical lead 20. It will be understood that the shape and dimensions of the ceramic body 12 will be dependent of the application, the desired ohmic resistance and the like. For many applications the body 12 will be a circular cylinder.

Referring to Fig. 2 of the drawing, there is illustrated the electrical properties 'of a series of barium strontium titanates and barium lead titanates, `all containing 0.01 mol of yttrium. It will be noted that the temperature at Iwhich the abrupt rise in electrical resistivity occurs is between 25 and 50 C. for the barium strontium titanates. The initial low resistivity assumes a value which is higher as the proportion of strontium increases. By substituting flead yfor a part of the barium the temperature at which the resistivity rapidly increases is shifted to approximately 120 to 130 C. Increasing the proportion of lead reduces the low temperature resistivity values in proportion thereto.

Ex'ample III Referring to Fig. 3 of the drawings there is illustrated the characteristic resistivity curves of a cerium barium strontium titanate, comprising 0.0037 mol of cerium, 0.852 mol of barium and 0.14 mol of strontium. The curve A was determined on a sample of the vitrified ceramic material which was produced by following the procedure set forth in Example I being concluded by aging 2 hours in air at 1260 C. It will be noted that the resistivity at vapproximately room temperature (25 C.) is 70 ohm centimeters. The resistivity at 50 C. is approximately 100 ohm centimeters; at 75 C. the resistivity is approximately 250 ohm centimeters and at 150 C. the resistivity is approximately 15,000 ohm centimeters. Curve B is that obtained by testing the composition which was only sintered in the argon atmosphere of 1390 C. The composition used in curve B was not aged in air at 1260 C. as was the material from which curve A was prepared. It will be noted that the room temperature resistivity value of material B is approximately 1000 ohms `and that the slope of the curve is much less than that of curve A. Consequently, the positive temperature coeflcient of resistance for room temperature to 150 C. is relatively moderate.

Example IV A ceramic body was prepared following the process of Example I employing the following composition: 0.99 mol barium, 0.01 yttrium and 1 mol of titanium oxide. Curve C of Fig. 4 indicates the electrical resistivity with change of temperatures. It will be noted that the resistivity at approximately 50 C. is approximately 1500 ohm centimeters. When the ceramic material is heated to temperatures of 100 C. and higher the resistivity increases with great rapidity. Thus, at 110 C. the resistivity is 4,000 ohm centimetersand at 150 C. the resis- .6 tivity'is in the neighborhood of 600,000 ohm centimeters. Such an abrupt change in'res-istivity renders the material employed for curve C in Fig. 4 highly useful for electrical control and temperature measuring devices.

In order to indicate the benefits ofthe air aging step of the process the same material employed for curve C in Fig. 4 was sintered at 1300 C. but was not aged i The electrical properties as shown in curve D indicate a negative temperature coefcient of quite low value. Thus t-he air aging converts a negative temperature coeteient to a very marked positive temperaturecoeticient.

It will be understood that the present specification and drawing are only illustrative and not limiting.

I claim as my invention:

1. A ceramic body having a positive temperature coeicient of electrical resistance over a selected range of temperatures, the body comprising the fired product composed essentially of 1.00 mol of titanium dioxide, and a total of one mol of (a) up to 0.999 mol of a barium oxide, barium strontium oxide, lead oxide, and barium lead oxide, and (b) a rare earth metal oxide selected from the group consisting of from 0.001 mol to 0.006 mol of cerium oxide and from 0.005 to 0.02 mol of yttrium oxide, the body being initially tired in an inert atmosphere to sinter it and thereafter fired in air at a temperature of at least 1000 C. for a period of hours.

2. A ceramic body having a positive temperature coefficient of electrical resistance over a selected range of temperatures, the body comprising the tired product comprising YxBa(1 x)TiO3 where x has a value of from 0.005 to 0.02, the body being initially tired in an inert atmosphere to sinter it and thereafter fired in air at a temperature of at least 1000 C. for a period of hours.

3. A ceramic body having a positive temperature coeflicient of electrical resistance over a selected range of temperatures, the body comprising the fired product comprising CexBa(1 x)TiO3 where x has a value of from 0.003 to 0.006, the body being initially tired in an inert atmosphere to sinter it and thereafter tired in air at a temperature of a least 1000 C. for a period of hours.

4. A ceramic body having a positive temperature coefcient of electrical resistance over a selected range of temperatures, the body comprising the tired product comprising YnBa(1 n x)PbxTiO3 where n has a value of from 0.005 to 0.02, and x has a value of from 0.01 to 0.25, the body being initially tired in an inert atmosphere to sinter it and thereafter tired in air at a temperature of at least 1000 C. for a period of hours.

5. A ceramic body having a positive temperature coeilicient of electrical resistance over a selected range of temperatures, the body comprising the fired product comprising YmBa(1 m x)Sr,'l`-i03 where m has a value of 0.005 to 0.02 and x has a value of from 0.01 to 0.30, the body being initially tired in an inert atmosphere to sinter it and thereafter tired in air at a temperature of at least 1000 C. for a period of hours.

6. A ceramic body having a positive temperature coefficient of electrical resistance over a selected range of temperatures, the body comprising the tired product comprising CenBa(1 n x PbxTiO3 Iwhere n has a lvalue of 0.005 to 0.02 and x has a value of from 0.01 to 0.30, the body being initially red in an inert atmosphere to sinter it and thereafter fired in air at a temperature of at least 1000 C. for a period of hours.

7. A ceramic body having a positive temperature coefficient of electrical resistance over a selected range of temperatures, the body comprising the fired product cornprising CenBa(1 n X)SrXTiO3 where n has a value of from 0.003 to 0.006, and x has a value of from 0.01 to 0.30, the body being initially tired in an inert atmosphere to sinter it and thereafter fired in air at a temperature of at least 1000 C. for a period of hours.

8. A thermistor device comprising a ceramic body having a positive temperature coefcient of electrical resistance over a selected range of temperatures, the body comprising the red product composed essentially of 1.00 mol of titanium dioxide, and a total of one. mol of (a) upto,V 0.999 mol of a..` barium oxide, barium strontium oxide, lead oxide, and barium lead4 oxide, and (b) a rare earth metal oxide selected from the group consisting of 5 :from 0.001 mol to 0.006 mol of cerium oxide and from 0.0051to. 0.02 molof yttrium oxide, the body being initially tired in an inert atmosphere to sinter it and thereafter red in air at a temperature of at least 1000 C. for a period of hours, eleetricalleads` affixed to the body by an ohmic 10 contact comprising a soldered joint.

References Cited inthe file of this patent UNITED STATES PATENTS Ehlers et al Apr. 9, 1946 Rath e Dec. 9, 1947 Johannes et al Jan. 6, 1948 Klasens Nov. 4, 1952 FOREIGN PATENTS Great Britain Sept. 8, 1954 Great Britain Aug. 7, 195.7 

